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JP4583173B2 - Quantitative analysis of conjugated dienes in hydrocarbon feedstocks and products as an indicator of fouling potential - Google Patents

Quantitative analysis of conjugated dienes in hydrocarbon feedstocks and products as an indicator of fouling potential Download PDF

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JP4583173B2
JP4583173B2 JP2004526035A JP2004526035A JP4583173B2 JP 4583173 B2 JP4583173 B2 JP 4583173B2 JP 2004526035 A JP2004526035 A JP 2004526035A JP 2004526035 A JP2004526035 A JP 2004526035A JP 4583173 B2 JP4583173 B2 JP 4583173B2
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キアン，カングナン
エドワーズ，キャスリーン，イー．
ワング，フランク，シー．
シスキン，マイケル
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Description

本発明は、炭化水素原料ストリームおよび生成物中の共役ジエンを定量する方法に関する。より詳しくは、本方法は、共役ジエンのモル濃度および／または炭素数分布を決定する。   The present invention relates to a method for quantifying conjugated dienes in hydrocarbon feed streams and products. More particularly, the method determines the molar concentration and / or carbon number distribution of the conjugated diene.

共役ジエンは、炭化水素系中の化合物の主要な分類であり、これは、水素化分解および水素転化装置などの精油所転化装置、並びに分留装置および熱交換器におけるデポジット形成の原因である。それらはまた、自動車のエンジンにおけるデポジット形成の原因である。炭化水素系におけるデポジット形成の可能性を評価する知見は、重大である。共役ジエンの濃度およびタイプに関する知識は、精油所原料を前処理する必要性に関して、精油所に指標を提供する。処理中にファウリングを防止するために、処理に先立ってジオレフィン飽和装置を設置する必要性などである。燃料への適用に際しては、この知見は、例えば、ナフサを燃料中に混合しうるか否か、およびどの程度混合しうるか、またはナフサを水素化処理する必要があるか否か、等を決定するのに用いうる。   Conjugated dienes are a major class of compounds in hydrocarbon systems, which are responsible for deposit formation in refinery conversion equipment, such as hydrocracking and hydroconversion equipment, as well as fractionation equipment and heat exchangers. They are also responsible for deposit formation in automobile engines. The knowledge that assesses the potential for deposit formation in hydrocarbon systems is critical. Knowledge of the concentration and type of conjugated diene provides an indication to the refinery regarding the need to pre-treat the refinery feedstock. In order to prevent fouling during processing, it is necessary to install a diolefin saturation device prior to processing. For fuel applications, this knowledge determines, for example, whether and how much naphtha can be mixed into the fuel, whether or not naphtha needs to be hydrotreated, etc. Can be used for

炭化水素系中の非環状および環状の共役ジエンを同定および定量するのに、信頼出来る確立された方法が全くない。ＧＣ／ＦＩＤ（水素炎イオン化検出器）は、低沸点の炭化水素系中の小さな共役ジエン（Ｃ６未満）を定量するのに用いうる。この同定は、保持時間および質量スペクトルライブラリーとの対比に基づいて為される。この方法は、分析対象の低い濃度、他の炭化水素成分との重度の重なり、並びに共役および非共役ジエンの極めて類似した質量スペクトルのために、大きな共役ジエン（Ｃ６超）を同定／定量することができない。 There is no reliable and established method for identifying and quantifying acyclic and cyclic conjugated dienes in hydrocarbon systems. GC / FID (flame ionization detector) may use the low boiling point of the small conjugate diene in the hydrocarbon-based (less than C 6) to quantify. This identification is made on the basis of retention times and comparison with mass spectral libraries. This method is low analyte concentration, the overlap of severe and other hydrocarbon components, as well as for very similar mass spectra of conjugated and non-conjugated dienes, to identify / quantify a large conjugated diene (C 6 greater) I can't.

臭素化は、広く、炭化水素中のオレフィン含有量（共役ジエンを含む）を決定するのに用いられた。それは、共役ジエンを他のオレフィンから区別することが出来ない。芳香族、特にフェノールが、分析を妨害することがある。   Bromination has been widely used to determine the olefin content (including conjugated dienes) in hydrocarbons. It cannot distinguish conjugated dienes from other olefins. Aromatics, especially phenols, can interfere with the analysis.

ＭＡＶ試験は、ＵＯＰによって開発された半定量方法であり、無水マレイン酸を誘導体化剤として用いる。反応は選択的でなく、また定量的に進行しないことがある。従って、相対的な数値しか得られない。加えて、それは、精油所の指標に必要な、共役ジエンタイプの異なる分子の同定が出来ない。   The MAV test is a semi-quantitative method developed by UOP and uses maleic anhydride as a derivatizing agent. The reaction is not selective and may not proceed quantitatively. Therefore, only relative numerical values can be obtained. In addition, it fails to identify molecules of different conjugated diene types that are required for refinery indicators.

本発明は、種々の炭化水素母材（スチーム分解ナフサ、接触分解ナフサ、コーカーナフサおよび他の石油留出油など）中の共役ジエンを検出し、同定し、更に定量する方法である。共役ジエンは、種々の精油所プロセスにおける分子量成長反応（ファウリング）の主要な原因である。   The present invention is a method for detecting, identifying and further quantifying conjugated dienes in various hydrocarbon matrices (such as steam cracked naphtha, catalytic cracked naphtha, coker naphtha and other petroleum distillates). Conjugated dienes are a major cause of molecular weight growth reactions (fouling) in various refinery processes.

本明細書に記載された本発明は、４−メチル−１，２，４−トリアゾリン−３，５−ジオン（ＭＴＡＤ）により、共役ジエンを選択的かつ迅速に室温で誘導体化し、次いで化学イオン化ＧＣ／ＭＳおよびＧＣ／ＮＣＤ分析することに基づく。本方法は、他の炭化水素成分に全く妨害されず、直鎖状、分枝状および環状の共役ジエンに対し顕著に選択的かつ鋭敏である。本発明は、スチーム分解および接触分解ナフサ中の共役ジエンについて、そのタイプおよび濃度を決定するのに好首尾に適用された。   The invention described herein is directed to selectively and rapidly derivatizing conjugated dienes at room temperature with 4-methyl-1,2,4-triazoline-3,5-dione (MTAD), followed by chemical ionization GC. Based on / MS and GC / NCD analysis. The process is totally uninterrupted by other hydrocarbon components and is significantly selective and sensitive to linear, branched and cyclic conjugated dienes. The present invention has been successfully applied to determine the type and concentration of conjugated dienes in steam cracking and catalytic cracking naphtha.

本発明は、燃料、石油原料および生成物中の痕跡レベルの共役ジエンを検知、同定、更に定量しうる方法である。これらの共役構造は、精油所装置における分子量成長反応（ファウリング）および自動車エンジンにおけるデポジット形成の主要な原因である。共役ジエンタイプの完全な同定／定量は、ファウリングの防止および管理に必要とされる。本方法には、次の工程が含まれる。即ち、（１）４−メチル−１，２，４−トリアゾリン−３，５−ジオン（ＭＴＡＤ）による共役ジエンの選択的・定量的な化学誘導体化、（２）化学イオン化ガスクロマトグラフ／質量分析法（ＣＩ ＧＣ／ＭＳ）による炭素数に応じたＭＴＡＤ−ジエン付加物の選択的・定量的な測定、および（３）ガスクロマトグラフ／窒素化学ルミネセンス検出器（ＧＣ／ＮＣＤ）などの窒素選択的検出器付きＧＣによる全共役ジエンの測定が含まれる。   The present invention is a method that can detect, identify and further quantify trace levels of conjugated dienes in fuels, petroleum feedstocks and products. These conjugated structures are a major cause of molecular weight growth reactions (fouling) in refinery equipment and deposit formation in automotive engines. Complete identification / quantification of conjugated diene types is required for fouling prevention and management. The method includes the following steps. (1) Selective and quantitative chemical derivatization of conjugated dienes with 4-methyl-1,2,4-triazoline-3,5-dione (MTAD), (2) Chemical ionization gas chromatography / mass spectrometry (CI GC / MS) Selective and quantitative measurement of MTAD-diene adduct according to carbon number, and (3) Nitrogen selective detection such as gas chromatograph / nitrogen chemiluminescence detector (GC / NCD) Measurement of total conjugated dienes by instrumented GC is included.

一般的手順
ＭＴＡＤ２５０ｍｇを塩化メチレン５ｍｌに溶解することによって、ＭＴＡＤ原液を調製した。原液を室温で炭化水素試料と直接混合して、共役構造を誘導体化した。ＭＴＡＤは、選択的かつ迅速に（通常＜５秒）、図５に示されるように、直鎖状および環状共役ジエンと反応する。 General Procedure An MTAD stock solution was prepared by dissolving 250 mg MTAD in 5 ml methylene chloride. The stock solution was directly mixed with the hydrocarbon sample at room temperature to derivatize the conjugated structure. MTAD reacts selectively and rapidly (usually <5 seconds) with linear and cyclic conjugated dienes, as shown in FIG.

シクロヘプタジエンを、定量のための内部標準として選択した。誘導体化した試料をＧＣ／ＮＣＤによって分析し、共役ジエンの全モル濃度を測定した。また並行して、誘導体化した試料をＧＣ／ＭＳによって分析し、共役ジエンの炭素数分布を測定した。重水素化アンモニア（ＮＤ３）を用いる化学イオン化（ＣＩ）によって、分子をイオン化した。重水素化された分子イオン［Ｍ＋Ｄ＋］およびＮＤ４付加物［Ｍ＋ＮＤ４ ＋］の選択されたイオン表示を、種々の共役ジエンを区別するのに用いた。 Cycloheptadiene was selected as an internal standard for quantification. Derivatized samples were analyzed by GC / NCD to determine the total molar concentration of conjugated dienes. In parallel, the derivatized sample was analyzed by GC / MS to determine the carbon number distribution of the conjugated diene. Molecules were ionized by chemical ionization (CI) using deuterated ammonia (ND 3 ). Selected ion representations of deuterated molecular ion [M + D + ] and ND 4 adduct [M + ND 4 + ] were used to distinguish the various conjugated dienes.

ＭＴＡＤは、直鎖状および環状の共役ジエンと１：１付加物を形成する。図１は、誘導体化前後におけるスチーム分解ナフサのＧＣ／ＭＳクロマトグラフを示す。保持時間２０分より後に現れる一連のピークは、ＭＴＡＤ反応生成物の形成によるものである。２０分より前のクロマトグラフィーのピークは、実質的に単純化された。これもまた誘導体化の指標である。スチレン、インデン、並びにＣＰＤおよびＭＣＰＤの二量体は、一部がＭＴＡＤと反応する。それらは、２６分超の保持時間にＭＴＡＤ付加物を形成する。非共役炭化水素は、前記実験条件下ではＭＴＡＤと反応しない。   MTAD forms 1: 1 adducts with linear and cyclic conjugated dienes. FIG. 1 shows a GC / MS chromatograph of steam-decomposed naphtha before and after derivatization. A series of peaks appearing after a retention time of 20 minutes is due to the formation of the MTAD reaction product. The chromatographic peak before 20 minutes was substantially simplified. This is also an indicator of derivatization. Styrene, indene, and CPD and MCPD dimers partially react with MTAD. They form MTAD adducts with retention times greater than 26 minutes. Non-conjugated hydrocarbons do not react with MTAD under the experimental conditions.

ジエン付加物の保持時間は主として、化合物の分子量よりも、むしろ極性に影響を及ぼされることが特記された。異なる炭素数を有する共役ジエンがクロマトグラフィー上で重なる可能性があるため、これは分析を複雑にした。共役ジエンを区別するには、ＧＣ／ＭＳが必要となる。   It was noted that the retention time of the diene adduct is primarily affected by polarity rather than the molecular weight of the compound. This complicates the analysis because conjugated dienes with different carbon numbers can overlap on chromatography. GC / MS is required to distinguish conjugated dienes.

ＭＴＡＤ：ジエンの比率
ＭＴＡＤ誘導体化に関するＭＴＡＤ添加の効果を、ＧＣ／ＮＣＤおよびＧＣ／ＭＳの両方によって評価した。モデル化合物１，３−ヘキサジエンの場合、ＭＴＡＤ／共役ジエンのモル濃度が２〜１０のとき、転化率１００％が達成される。比率が２未満の場合には、ＭＴＡＤ反応は不完全である。比率が１０超の場合には、ＭＴＡＤの自己重合が支配的になり、ＭＴＡＤ−共役ジエン付加物が低減される。 MTAD: diene ratio The effect of MTAD addition on MTAD derivatization was evaluated by both GC / NCD and GC / MS. In the case of the model compound 1,3-hexadiene, a conversion rate of 100% is achieved when the MTAD / conjugated diene molar concentration is 2-10. If the ratio is less than 2, the MTAD reaction is incomplete. When the ratio is more than 10, MTAD self-polymerization becomes dominant and MTAD-conjugated diene adduct is reduced.

実際の試料分析において、過剰なＭＴＡＤ添加はより大きな問題となる。それは、共役ジエンによらないＭＴＡＤ誘導体の形成をもたらす。定量分析には、ＭＴＡＤ：共役ジエンの最適比率は２〜３．５であると結論付けられる。   In actual sample analysis, excessive MTAD addition becomes a bigger problem. It leads to the formation of MTAD derivatives that do not depend on conjugated dienes. For quantitative analysis, it is concluded that the optimal ratio of MTAD: conjugated diene is 2-3.5.

相対感度
初めに、共役ジエンの１２種のモデル化合物の相対感度を、ＧＣ／ＮＣＤ、ＧＣ／ＦＩＤおよびＥＩ−ＧＣ／ＭＳによって評価した。ＧＣ／ＮＣＤは、全く一様な応答を示す。しかし、ＥＩ−ＧＣ／ＭＳの分子イオン強度は相当に異なる。ＣＩは、ＥＩほどには分子をフラグメント化しないソフトイオン化法なので、ＣＨ４およびＮＤ３を試薬ガスとして用いるＣＩ−ＧＣ／ＭＳを、５種の選択されたモデル化合物に対して評価した。感度係数の変動は確かに低減され、より予想可能になる。いずれの試薬ガスも、類似の相対感度係数をもたらす。ＣＨ４ ＣＩにおいては、分子は、プロトン化分子イオン［Ｍ＋Ｈ＋］およびエチルカチオン付加物［Ｍ＋Ｃ２Ｈ９ ＋］を形成する傾向がある。これは、異なる炭素数を有するジエンに対して、質量のオーバーラップをもたらす可能性がある（例えば、Ｃ５＋Ｃ２Ｈ９ ＋はＣ７＋Ｈ＋とオーバーラップする）。ＮＤ３ ＣＩは、問題がなく、分析のために選択された。 Relative sensitivity Initially, the relative sensitivity of 12 model compounds of conjugated dienes was evaluated by GC / NCD, GC / FID and EI-GC / MS. GC / NCD shows a completely uniform response. However, the molecular ionic strength of EI-GC / MS is quite different. Since CI is a soft ionization method that does not fragment molecules as much as EI, CI-GC / MS using CH 4 and ND 3 as reagent gases was evaluated against five selected model compounds. Sensitivity coefficient variation is certainly reduced and becomes more predictable. Either reagent gas provides a similar relative sensitivity factor. In CH 4 CI, the molecules tend to form protonated molecular ions [M + H + ] and ethyl cation adducts [M + C 2 H 9 + ]. This can result in mass overlap for dienes with different carbon numbers (eg, C 5 + C 2 H 9 + overlaps with C 7 + H + ). ND 3 CI was fine and was selected for analysis.

共役ジエン構造の決定
本方法は、いかなる既存技術によっても得られない共役ジエンの構造的な知見を提供する。共役ジエン付加物の質量スペクトルは、二重結合の位置およびその化学的な環境に特徴的である。図２は、１，３−ペンタジエン、２，４−ヘキサジエンおよび２，４−ヘプタジエン（ｈｅｐｔａｄｉｅｎｅ）のＭＴＡＤ付加物の質量スペクトルを示す。 Determination of Conjugated Diene Structure This method provides structural knowledge of conjugated dienes that cannot be obtained by any existing technology. The mass spectrum of a conjugated diene adduct is characteristic of the position of the double bond and its chemical environment. Figure 2 shows 1,3-pentadiene, a mass spectrum of 2,4-hexadiene and 2,4 MTAD adduct heptadiene (hep ta diene).

ナフサ試料の分析
ＭＴＡＤ方法は、Ｃ１０以下の共役ジエンを検出可能である。本方法を、種々のナフサ試料に適用した。図３は、スチーム分解ナフサ（ＳＣＮ）二種、即ち未処理および水素化処理された試料における共役ジエン分布を示す。殆どの共役ジエン（非環状および環状の両方）は、これらのＳＣＮ試料においてＣ５〜Ｃ７である。これは、ＧＣ／ＦＩＤには表れない。 Analysis MTAD method naphtha sample is capable of detecting the of C 10 or less of conjugated diene. The method was applied to various naphtha samples. FIG. 3 shows the conjugated diene distribution in two steam cracked naphtha (SCN) samples, namely untreated and hydrotreated. Most of the conjugated diene (both acyclic and cyclic) are C 5 -C 7 In these SCN samples. This does not appear in GC / FID.

図４は、重質接触ナフサ（ＨＣＮ）三種における、共役ジエンに関する分布の類似の組を示す。これらの試料において、殆どの共役ジエン（非環状および環状の両方）はＣ７ ＋である。 FIG. 4 shows a similar set of distributions for conjugated dienes in three heavy contact naphtha (HCN) species. In these samples, most conjugated dienes (both acyclic and cyclic) are C 7 + .

スチーム分解ナフサ（ＳＣＮ）＋シクロヘプタジエン内部標準についての、ＭＴＡＤ誘導体化前後におけるＧＣ／ＭＳクロマトグラムを示す。FIG. 5 shows GC / MS chromatograms before and after MTAD derivatization for steam cracked naphtha (SCN) + cycloheptadiene internal standard. ２，４−ヘプタジエン、２，４−ヘキサジエンおよび１，３−ペンタジエンのＭＴＡＤ付加物についてのＧＣ／ＭＳスペクトル（電子衝撃）を示す。2 shows GC / MS spectra (electron impact) for MTAD adducts of 2,4-heptadiene, 2,4-hexadiene and 1,3-pentadiene. スチーム分解ナフサ（ＳＣＮ）二種における共役ジエン分布を示す。The conjugated diene distribution in two steam cracked naphtha (SCN) species is shown. 重質接触ナフサ（ＨＣＮ）三種における共役ジエン分布を示す。The conjugated diene distribution in three heavy contact naphtha (HCN) species is shown. ＭＴＡＤと、直鎖状および環状共役ジエンの反応スキームを示す。2 shows the reaction scheme of MTAD with linear and cyclic conjugated dienes.

Claims (5)

原料または生成物ストリーム中の共役ジエンを定量する方法であって、
（ａ）前記原料または生成物ストリームに、４−メチル−１，２，４−トリアゾリン−３，５−ジオン（ＭＴＡＤ）を、ＭＴＡＤ：原料または生成物ストリーム中の共役ジエンの比率が２〜１０となる割合で、溶解する工程
（ｂ）前記原料または生成物ストリームに、定量標準として参照化合物を導入する工程、
（ｃ）前記共役ジエンのモル濃度および前記共役ジエンの炭素数分布をＮＤ３化学イオン化ガスクロマトグラフ／質量分析法（ＮＤ３ ＣＩ ＧＣ／ＭＳ）により決定する工程、
および
（ｄ）ガスクロマトグラフ／窒素化学ルミネセンス検出器（ＧＣ−ＮＣＤ）により全共役ジエンを定量する工程
を含み、
かつ、その際、環状および非環状の全てのＭＴＡＤ−共役ジエン分子は、ＮＤ３化学イオン化に際して、Ｍ＋Ｄ＋およびＭ＋ＮＤ４ ＋イオンを形成することを特徴とする共役ジエンの定量方法。A method for quantifying conjugated dienes in a raw material or product stream comprising:
(A) 4-methyl-1,2,4-triazoline-3,5-dione (MTAD) is added to the raw material or product stream, and the ratio of MTAD: conjugated diene in the raw material or product stream is 2 to 10 (B) introducing a reference compound into the raw material or product stream as a quantitative standard,
(C) determining the molar concentration of the conjugated diene and the carbon number distribution of the conjugated diene by ND 3 chemical ionization gas chromatography / mass spectrometry (ND 3 CI GC / MS);
And (d) quantifying total conjugated dienes by gas chromatograph / nitrogen chemiluminescence detector (GC-NCD),
And, at that time, all cyclic and acyclic MTAD-conjugated diene molecules form M + D + and M + ND 4 + ions upon ND 3 chemical ionization. ＭＴＡＤ：共役ジエンの比率は、２〜３．５であることを特徴とする請求項１に記載の共役ジエンの定量方法。  The method for quantifying conjugated diene according to claim 1, wherein the ratio of MTAD: conjugated diene is 2 to 3.5. ＭＴＡＤ−共役ジエン付加物の異性体成分を分離するのに、オンラインガスクロマトグラフを用いることを特徴とする請求項１に記載の共役ジエンの定量方法。  The method for quantifying a conjugated diene according to claim 1, wherein an on-line gas chromatograph is used to separate the isomer components of the MTAD-conjugated diene adduct. ＭＴＡＤ−共役ジエン付加物の相対感度を測定し、ＮＤ３ ＣＩ ＧＣ／ＭＳの応答の補正に適用することを特徴とする請求項１に記載の共役ジエンの定量方法。The relative sensitivity of MTAD-conjugated diene adduct is measured, and applied to correction of ND 3 CI GC / MS response, The method for quantifying conjugated diene according to claim 1. １０以下の炭素数分布を測定することを特徴とする請求項１に記載の共役ジエンの定量方法。  The method for quantifying conjugated dienes according to claim 1, wherein a carbon number distribution of 10 or less is measured.
JP2004526035A 2002-08-06 2003-07-08 Quantitative analysis of conjugated dienes in hydrocarbon feedstocks and products as an indicator of fouling potential Expired - Fee Related JP4583173B2 (en)

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